Vat dyestuff of the anthracene series.



TED "STATES; PATENT OFFICE.

rrunnmcn smenn, or OFFENBACHONTHE-MAIN, GERMAN-Y, nssronon- TO conro- RATION or. crmmscnn FABRIK GRIESHEIM-ELEKTRON, or FRANKFOR'I..-ON-.THE- L MAIN GERMANY.

var nyns'rurr' or THE ANTHRACENE SERIES.

No Drawing.

To all whom it may concern:

Be it known that I, FRIEDRICH SINGER, doctor of philosophy, chemist a subject of the German Emperor, and resident of Oifenbach-on the-Main, in the Grand Duchy of Hesse, Germany, with the post-ofiice address N o. 17 9 Mainstrasse, have invented new and useful Improvements in Vat Dyestuffs of the Anthracene Series, of which the following is a specification. e

I have discovered that new-valuable vat dyestuffs can be obtained by heating the products of reduction of anthraqumone, which result by condensation of two anthraquinone molecules on the meso-carbon-atom, as for instance dianthrone, rdianthran'ole, biant-hrone with condensingagents in presence of or without a diluent. "As condensing agents may be used aluminium chlorid, ferric chlorid antimony pentaehlorid, chromie chlorid, sulfuric acid, chlorid of zinc, mercuric-chlorid, stannic chlorid, and analogous acting "substances.

The structural formulae of the starting bodies are the following:

Bianthrone. Dianthrone.

The new dyestuffs dye cotton from alkaline hydrosulfite vat brown shades of very good properties as to fastness.

The following examples will serve to illustrate the natilre of my invention and how Diauthranole.

Ill

. it can be carried out; parts being by wei'glit. O

Example I: 20 parts of dianthrone tained by oxydation of anthranole w th ferric chlorid, in glacial acetic acid solut on: sparkling prisms of 245 C. meltmg'pomt) are suspended'in 200 parts of nitrobenzene, whereupon 20 parts of ground Sublimated aluminium chlorid are added. The solution being green in the beginning, turns intens ve red at a temperature of120 C. under V10- lent evolution of hydrochloric oacid. Theformation of dyestuif is completed after heating from 140 to 160 C. during 10 Specification of Letters Patent.

hours. The nitrobenzene is'isepa'rated by passing through a current of steam. The

remaining part is boiled out successively with hydrochloric acid, water and alcohol.

The dyestufli is a brown black powder,*solu ble in concentrated sulfuric acid with 'brown Patented Aug; 1,1911; I Application filed December 8, 1910. Serial No. 596,250. l

violet color. It yields by treatment 'with alkaline hydrosulfite a- 'garnet-brown' vat dyelng cotton garnet-brown shades which,

after rinsing and soaping, are converted in chocolate-brownones of very good-fastness.

According-to the quantity of aluminium Chl01ld, l1$(.l in the process and the tempera ture maintained dyestufi's of rather more green, respectively more red' tint are obtamed.

Example II: 20,parts'of bianthrone (obtained by reduction of anthraquinone with zmc dust'and caustic soda lye under pressure line solution with sodium .hypochlorit':

at 160 and subsequent oxidationof'the alka I lemon colored compact crystals) are dissolved in nitrobenz'ene. 13 parts .fof aluminium chlorid are added, Where'by the solution turns red. After heating up .from.140'to 160 the formation of dyestuif is-completed. The dyestufi is finished as described in. Example I. It is a brown-black powder; soluble in concentrated sulfuric acidwith. violet+brown color. Ityields by treatment with alkaline hydrosulfit solution a brown. iolet vat, dyeing cotton reddish brouze-brown shades. The quantity and quality (proportion of. oxychlorid) of the aluminiumelilorid'used.

in this process and the'temperaturermaintained, are of influence upon-the formation of dyestufl.

Example III: From 20 parts of bianthrone and 20 parts offaluminium chlorid at temperatures from 80 to C. a greenblack' dyestufi' 'is obtained, vsoluble in com centrated sulfuricacid with bright blue-red color, and yielding a brown-red vat, dyeing cotton. olive brown shades.-

Example IV: 20 parts of bianthrone, 20

parts of Sublimated ferric chlorid and 200.

parts of boiled out nitrobenzene are heated together up to 140 during 14 hours. The resulting dyestuii' is a black powder, soluble inconcentrated sulfuric acid with brownviolet color dyeing cotton from the garnetbrown va't greenish-bronze-brown shades.

Exe'np V; In 200 parts of dry nitrobenzene. an introduced while'stirring successively 40 parts of bianthrone and 50 parts of antimony pentachlorid. The solution being green in the beginning, turns intensive introduced in 400 parts'of sulfuric acid B. and cautiously heated up to 120. 'As soon as the evolution of sulfurous acid ceases the melt is poured in cold water, boiled out, the separated dyestuif isolated by filtration and washed with water. The thus obtained grey-black powder dissolves in concentrated {sulfuric acid with brown-red color and yields by treatment with alkaline 'hydrosulfit a brown-violet vat, dyeing cotton bronzebrown shades. Instead of sulfuric acid 60 B.,su1furic acid of 66 B. or a more diluted one may be used. Instead of 120 C. a temperature of 180 may be maintained.

Dianthranole and :biant-hrone may be also v used for the manufacture of vat dyestuffs in the manner described in Example VI.

In the following table the properties of some of the dyestuffs are given:

Dyestufi ob- Ata tem' erature solution Solution in alka- Dyes uumortained from- Bycmdensmg wm1 'oi Appearance gfgfg g line hydrosulfite. duntcd cottou- Dianthrone. Sulfuric acid 66 B Black... Reddish brown. Gre -brown Grcyflirown. Dmnthronm. Sulfuric acid60B Grey-blue Brown-red Vio et-brown... Bronze-brown. Dlanthrone Sulfuric acid60B Grey-black... Green bmwn... Brown-black... Rgddish-greyrown. Dianthrone Aluminium chlorid...... Brown-black. Brown-violet... Gamctrbrown" Chocolatc-brown. Dienthrone sulfuric acid 60B 120 Grey-black... Brown-violet... Garnet-brown.. Bronze-brown. Bianthrone Ferric chlorid Black...;....'l Brown-violet... Garnet-brown.. Grccnish-bronzc- I rown. Bianthrone pelrcednt.ofa1uminium Brown-black. Violetbrown... Violct'brown... Hamish-bronzec or; rown. Bianthrone erlcleintofaiuminium Green-black.. Brigeit brown- Brigit brown- Olive-brown;

c o a r re Bianthrone.. Antimonypentachl0rid.. Black-brown. Yellow-brown.. Garnct-brown.. Reddismdrab. Dianthmno1e.... Aluminiumchlori Brown-black. Brown-violet... Violet-brown... Greenish-qmb. Dianthranole.... Sulfuric acid 66 B B1ack Brown-violet... Violet-brown... Rgddish-bronzcrown.

.Now what I claim and desire to secure by Letters Patent is the following:

1. The process for the manufacture of vat dyestuffs of the anthracene series, consisting in heating the products of reduction of anthraquinone, which result by condensation of two molecules of anthraquinone on the meso-carbon-atom, with condensing agents.

2. The process for manufacturing vat dye stuffs of the anthracene series, consisting in heating dianthrone with condensing agents.

3. The process for manufacturing a new vat dyestuff of the anthracene series, consistingin heating dianthrone with aluminiumchlorid.

V 4:- The rocess for the manufacture of a new vat yestufi' of the anthracene series, consisting V in heating dianthrone with aluminium chlorid in presence of a diluent.

5. The process for manufacturing a new vat dyestufi of the anthracene series, consisting in heating dianthrone with aluminium chlorid in presence of nitrobenzene .as diluent.

6. As anew article the vat dyestuif of the anthracene series, obtainable by heating dianthrone with aluminium-chlorid in presence of nitro-benzene, which dyestuff is a brown black-,powder soluble in concentrated sulfuric acid with brown violet color, in concentrated nitric acid with the same color but .with destruction of the dyestuil easily soluble in a warm solution of sodium sulfid with violet-brown color, yielding by treatment with alkaline hydrosulfite solution a garnet-brown vat, dyeing cotton garnet brown shades which, after rinsing and soaping, are converted into chocolate-brown ones of very good fastness. In testimony, that I claim the foregoing v as my invention, I have signed my name in presence of'two witnesses, this twenty-fifth day of November 1910.

FRIEDRICH SINGER.

Witnesses Eva LATTLER,.. I'IERMAN Wain. 

